Naphthalimide hydrazinamides

ABSTRACT

A NAPHTHALIMIDE DERIVATIVE HAVING THE FORMULA   1,3-DI(O=),2-X,6-(R-O-)-2,3-DIHYDRO-1H-BENZ(DE)   ISOQUINOLINE   WHEREIN R IS AN ALKYL, A CYCLOALKYL, AN ARALKYL, A HALOALKYL, AN ALKOXYALKYL, A HYDROXYALKYL, AN N,N-DIALKYLAMINOAALKYL, AN UNSUBSTITUTED OR HALOGEN-, ALKYL-, ALKOXY- OR HYDROXY-SUBSTITUTED ARYL, OR AN AMMONIUMALKYL; X IS A GROUP OF THE FORMULA,   -N&lt;(-C(=O)-A-C(=O)-)   WHEREIN A IS   -CH=CH-, -CH=C(-CL)-, -CH=C(-BR)-, -CH2-CH2-   OR AN UNSUBSTITUTED OR HALOGEN-SUBSTITUTED ARYLENE, OR A GROUP OF THE FORMULA,   -N(-R1)-Y-R2   WHEREIN R1 IS HYDROGEN, AN ALKYL, PHENYL, A HYDROXYALKYL, OR AN ALKOXYALKYL; Y IS -CO-, -COO-, -CONR3- (WHERE R3 IS HYDROGEN OR AN ALKYL), OR -SO2-; R2 IS HYDROGEN, AN ALKYL, A CYCLOALKYL, AN ARALKYL, A HALOALKYL, AN ALKYL- OR ARYL-SUBSTITUTED AMINOALKYL, AN UNSUBSTITUTED OR HALOGEN-, ALKYL-, ALKOXY-, HYDROXY-, AMINO- OR ALKYLAMINO-SUBSTITUTED ARYL, A GROUP OF THE FORMULA,   (1,3-DI(O=),6-(R-O-)-2,3-DIHYDRO-1H-BENZ(DE)   ISOQUINOLIN-1-YL)-N(-R1)-Y-R4-   (WHERE R, R1 AND Y ARE AS DEFINED ABOVE AND R4 IS BIVALENT GROUP), OR A GROUP OF THE FORMULA,   -R5-Q+.A-   (WHERE R5 IS DIRECT LINKAGE OR A BIVALENT GROU;; Q; IS A SUBSTITUTED AMMONIUM, A CYCLOAMMONIUM OR A HYDRAZINIUM; AND A- IS AN ANION), WHICH IS USEFUL FOR OPTICALLY BRIGHTENING AN ORGANIC POLYMER MATERIAL.

nit statgs 3,798,224 Patented Mar. 19, 1974 US. Cl. 260-281 3,798,224 NAPHTHALIMIDE HY DRAZINAMIDES Seiji Hotta, Hirakata, and Takashi Akamatsu, Ashiya,

Japan, assignors to Sumitomo Chemical Company,

Limited, Osaka, Japan No Drawing. Filed Dec. 22, 1970, Ser. No. 100,816

Claims priority, application Japan, Dec. 30, 1969, 45/1,862, 45/1,863, 45/1,864, 45/1,865, 45/1,866; May 8, 1970, 45/39,536; May 23, 1970, 45/44,291; July 15, 1970, 45/62,427; Sept. 18, 1970, 45/82,- 103, 45/82,104; Nov. 6, 1970, 45/98,113; Nov. 12, 1970, 45/ 100,011, 45/100,012, 45/ 100,013

Int. Cl. C07d 39/00 3 Claims ABSTRACT OF THE DISCLOSURE A naphthalimide derivative having the formula wherein R is an alkyl, a cycloalkyl, an aralkyl, a haloalkyl, an

alkoxyalkyl, a hydroxyalkyl, an N,N-dialkylaminoalkyl, an unsubstituted or halogen-, alkyl-, alkoxyor hydroxy-substituted aryl, or an ammoniumalkyl; X is a group of the formula,

wherein A is CH=CH--, CH=C, -CH=C, CHz-CH or an unsubstituted or halogen-substituted arylene, or a group of the formula,

atata Q \(m (where R, R and Y are as defined above and R is a bivalent group), or a group of the formula,

(where R is direct linkage or a bivalent group; Q+ is a substituted ammonium, a cycloammonium or a hydrazinium; and ais an anion),

which is useful for optically brightening an organic polymer material.

This invention relates to novel naphthalimide compounds and to a process for optically brightening organic polymers with the compounds.

This invention provides a novel naphthalimide com- 5 pound represented by the formula,

wherein R is an alkyl, a cycloalkyl, an aralkyl, a haloalkyl, an alkoxyalkyl, a hydroxyalkyl, an N,N-dialkylaminoa1kyl, an unsubstituted or halogen-, alkyl-, alkoxyor hydroxy-substituted aryl, or an ammoniumalkyl; X is a group of the formula,

or an unsubstituted or halogen-substituted arylene, or a group of the formula,

Y-Ra wherein R is hydrogen, an alkyl, phenyl, a hydroxyalkyl, or an alkoxy-alkyl; Y is -CO-, --C0O-, CONR (where R is hydrogen or an alkyl), or S0 R is hydrogen, an alkyl, a cycloalkyl, an aralkyl, a haloalkyl, an alkylor aryl-substituted aminoalkyl, an unsubstituted or halogen-, alkylalkoxy-, hydroxy-, aminoor alkylamino-substituted aryl, a group of the formula,

(where R, R and Y are as defined above and R is a bivalent group), or a group of the formula,

(where R is direct linkage or a bivalent group; Q+ is a substituted ammonium, a cycloammonium or a hydrazinium; and ais an anion).

The term, a1kyl," used in the present specification means an alkyl having 1 to 6 carbon atoms.

Also, a bivalent group represented by R is exemplified by an aliphatic chain such as an unsubstituted or halogenor alkyl-substituted alkylene (C -C CH NHCH CH CH CH CH SO CH CH CH=CH-CH etc.; an unsubstituted or alkyl-, N-alky1carbamoyl-, amidoor phenoxyimido-substituted phenylene such as -CH --oonnomomcm- NHCOCH-, 0 NHoocm- (51 All This invention also provides a process for preparing the naphthalimide compound having the Formula I, which comprises (1) reacting a compound of the formula,

N HR:

OT TO wherein R and R are as defined above, with a cyanate,

an isocyanic acid derivative, an acid halide of the formula,

R --YZ (III) ZY-R -YZ (IV) or an acid anhydride of the formula,

R2YO-YR2 (V) or i oo A 0 oo v1 (in the above formulas, Z is halogen and R R Y and A are as defined above), or (2) reacting a compound of the formula,

i N T 5 wherein X and Z are as defined above, with a compound of the formula,

(VII) ROI-l (VIII) wherein R is as defined above, or (3) reacting a compound of the formula,

i N O O I OH (IX) wherein X is as defined above, with an alkylating agent, or (4) reacting a compound of the formula,

wherein R R Y and Z are as defined above and n is an integer of 1 or 2 or the formula,

N 0 To wherein R is a haloalkyl and R R and Y are as defined above, with an amine or hydrazine and then reacting the resulting naphthalimide derivative with an alkylating agent or a quaternizing agent, if necessary.

The present invention is explained below in more detail.

( PROCESS (1 Examples of a compound of the Formula II are as follows:

N-amino-4-methoxynaphth alimide N-amino-4-ethoxynaphthalirnide N-amino-4-propoxynaphthalimide N-amino-4-butoxynaphthalimide N-amino-4- (Z-methoxyethoxy) naphthalimide N-amino-4- 2-ethoxyethoxy) naphthalimide N-amino-4- Z-butoxyethoxy) naphthalimide N-amino-4- (3 -chloro -2-hydroxypropoxy) naphthalimide N-amino-4-benzyloxynaphthalimide N-amino-4-phenoxynaphthalimide N-amino-4- (p-methylphenoxy) naphthalimide N-amino-4- (p-chlorophenoxy) naphthalimide N-amino-4- (p-methoxyphenoxy) naphthalimide N-amino-4- (rn-methylphenoxy naphthalimide N-methylamino-4-methoxyn aphthalimide N-rnethylamino-4-eth0xynaphth alimide N-methylamino-4-propoxynaphthalirnide N-rnethylamino-4-butoxynaphtha1imide N-methylamino-4isopropoxynaphthalimide N-methylamino-4-isobutoxynaphth alimide N-methylamino-4-benzyloxynaphthalimide N-methylarnino-4-phenoxynaphthalimide N-methylamino-4- (p-chlorophenoxy) naphthalimide N-methylamino-4- (m-methylphenoxy) naphthalimide N-methylamino-4- (p-methoxyphenoxy) naphthalimide N-methylamino-4- (Z-naphthyloxy) naphthalimide N-methylamino-4- (Z-methoxyethoxy naphthalimide N-methylarnino-4- (Z-ethoxyethoxy) naphthalimide N-methylamino-4- Z-butoxyethoxy) naphthalimide N-methylamino-4- (Z-hydroxyethoxy) naphthalimide N-methylamino-4- (3 -chloro-2-hydroxypropoxy) naphthalimide N-ethylamino-4-methoxynaphthalimide N-ethylamino-4-ethoxynaphthalimide N-ethylamino-4-butoxyn aphthalimide N-ethylamino-4-benzyloxynaphthalimide N-ethylamino-4-phenoxynaphthalimide N-ethylamino-4- (m-methoxyphenoxy) naphthalimide N-ethylamino-4- (o-methylphenoxy) naphthalimide N-ethylamino-4- (2,4-dimethylpheuoxy) naphthalimide N-ethylamino-4- Z-methoxyethoxy) naphthalimide N-ethylamino-4- Z-butoxyethoxy) naphth alimide N-ethylamino-4- (Z-diethylaminoethoxy) naphthalimide N-propylamino-4-methoxynaphthalimide N-propylamino-4-ethoxynaphth alimide N-propylamino-4-propoxynaphthalimide N-propylarnino-4-butoxynaphthalimide N-propylamino-4-phenoxynaphthalimide N-propylamino-4- (2-methoxyethoxy) naphthalimide N-propylamino-4- (2-butoxyethoxy naphthalimide N-buty1amino-4-methoxynaphthalimide N-butylamino-4-ethoxynaphthalimide N-butylamino-4-butoxynaphthalimide N-butylamino-4-phenoxynaphthalimide N-butylamino-4-(2-methoxyeflhoxy)naphthalimide N- (Z-hydroxyethylamino -4-methoxynaphthalimide N- Z-hydroxy ethylamino -4-ethoxynaphthalimide N- (Z-hydroxyethylamino -4-butoxynaphthalimide N-(2-hydroxyethylamino)-4-phenoxynaphthalimide N- (Z-thydroxyethylamiuo -4- (Z-methoxyethoxy) naphth alimide N- (2-hydroxyethylamino) -4- (Z-butoxyethoxy) n aphthalirnide N- (Z-hydroxyethylamino) -4- (p-hydroxyphenoxy) napnthalimide N- 2-methoxyethylamino) -4-methoxynaphthalimide N- (Z-methoxyethylamino) -4-ethoxynaphthalimide N- Z-methoxyethylarnino) -4-phenoxynaphthalimide N-(2-methoxyethylamino)-4- (Z-methoxyethoxy) naphthalimide N- Z-ethoxyethylamino) -4-methoxynaphthalimide N- 2-ethoxyethylamino -4ethoxynaphthali1nide N- 2-ethoxyethylamino -4-phenoxynapnthalimide N- (2-ethoxyethylamino -4- (2-ethoxyethoxy) naphthalimide N- (Z-ethoxyethylamino -4- (Z-butoxyethoxy) naphthalimide Examples of a cyanate and an isocyanic acid drivative are as follows:

Hexamethylene diisocyanate Potassium cyanate Methyl isocyanate Ethyl isocyanate Propyl isocyanate Butyl isocyanate Cyclonexyl isocyanate Phenyl isocyanate p-Tolyl isocyauate Benzyl isocyanate Toluylene diisocyanate Xylylene diisocyanate Hexamethylene diisocyanate Examples of an acid halide of the Formula III or IV are as follows:

Acetyl chloride Acetyl bromide Acetyl iodide Chloroacetyl chloride Bromoacetyl chloride Propionyl chloride Butyryl chloride Isobutyryl chloride Cyclohexane carbonyl chloride Benzoyl chloride Benzoyl bromide p-Anisoyl chloride p-Chlorobenzoyl chloride m-Chlorobenzoyl cnloride o-Chlorobenzoyl chloride 2,4-dichlorobenzoy1 chloride p-Toluyl chloride m-Toluyl chloride o-Toluyl chloride Terephthaloyl dichloride Isophthaloyl dichloride Fumaroyl dichloride Malonyl dichloride Succinyl dichloride Adipoyl dichloride Acryloyl cnloride Methacryloyl chloride Cinnamoyl chloride Furoyl chloride Nicotinyl chloride Methyl chloroformate Ethyl chloroformate Phenyl chloroformate Dimethylcarbamoyl chloride Diethylcarbamoyl chloride Methanesulfonyl chloride Ethanesulfonyl cnloride Ethanesulfonyl bromide Benzenesulfonyl chloride Tosyl chloride p-Chlorobenzenesulfonyl chloride 1,3-benzenedisulfonyl dichloride 4-chloro-1,3-benzenedisulfonyl dichloride Examples of an acid anhydride of the Formula V or VI are as follows:

Acetic anhydride Propionic anhydride Butyric anhydride Isobutyric anhydride Valerie anhydride Hexanoic anhydride Cyclohexa ecarboxylic anhydride Benzoic an ydride Succinic anhydride Maleic anhydride Phthalic anhydride Naphthalic anhydride Dichlorophthalic anhydride Tetraohlorophthalic anhydride Trimellitic anhydride Pyromellitic anhydride The present Compound I may be obtained by heating a mixture of a compound of the Formula II with a cyanate or an isocyanic acid derivative or a compound of the Formula III, IV, V or VI at a suitable temperature within a range from 0 to 200 C. in the presence or absence of water, acetic acid or an alcoholic solvent such as methanol, ethanol, etc., a ketone solvent such as acetone, methyl isobutyl ketone, etc., an aromatic solvent such as benzene, toluene, chlorobenzene, etc. or an amide solvent such as dimethylformamide, dimethylacetamide,

(2) PROCESS (2) Examples of a compound of the Formula VIII are as follows:

N-acetylamino-4-chloronaphthalimide N-b enzoylamino-4-chloronaphthalimide N-toluylamino-4-chloronaphthalimide N-propionylamino-4-chloronaphthalimide N-butyrylamino-4-chloronaphthalimide N- (p-chlorobenzoyl) amino-4-chloronaphthalimide N- (o-chlorobenzoyl) amino-4-chloronaphthalimide N-phthalimido-4-chloronaphthalimide N-dichlorophthalimido-4-chloronaphthalimide N-naphthalimido-4-chloronaphthalimide N-acetylamino-4-bromonaphthalimide N-benzoylamino-4-bromonaphthalimide N- methylacetylamino -4-chloronaphthalimide N- (methylacetylamino -4-bromonaphthalimide N- (ethylacetylamino -4-chloronaphthalimide N- (ethylacetylamino -4-bromonaphthalimide N- (propylacetylamino -4-chloronaphthalimide N- (butylacetylamino) -4-chloronaphthalimide N- (2-hydroxyethylacetylamino -4-chloronaphthalimide N- (methylpropionylamino -4-chloronaphthalimide N- (methylbutyrylamino) -4-chloronaphthalimide N- (ethylbutyrylamino -4-chloronaphthalimide N- (methylcyclohexanecarbonylamino -4-chloronaphthalimide N- (methylbenzoylamino) -4chloronaphthalimide N- (ethylbenzoylamino -4-chloronaphthalimide N- (ethylbenzoylamino )-4-bromonaphthalimide N- (propylbenzoylamino -4-bromonaphthalimide N- (butylbenzoylamino) -4-bromonaphthalimide N- (Z-methoxyb enzoylamiuo) -4-chloronaphthalimide N- (methyl-p-toluylamino) -4-bromonaphthalimide N- (ethyl-p-toluylamino -4-bromonaphthalimide N- (methyl-m-toluylamino) -4-chloronaphth alimide N- (methyl-o-toluylamino -4chloronaphthalimide N- (methyl-p-chlorob enzoylamino -4-chloronaphthalimide N- (ethyl-p-chlorobenzoylamino) -4-chloronaphthalimide N- (methyl-2,4-dichlorobenzoyl amino -4-bromonaphthalimide N-(methylanisoylamino -4-bromonaphthalimide N- (methylacryloylamino) -4-bromonaphthalimide Examples of a compound of the Formula VIII are as follows:

Methanol Ethanol Propanol 2-propanol Butanol Isobutyl alcohol Allyl alcohol Benzyl alcohol Phenethyl alcohol Ethylene glycol Propylene glycol Z-methoxyethyl alcohol 2,-ethxyethyl alcohol 2-butoxyethyl alcohol Z-diethylaminoethyl alcohol Phenol o-Cresol m-Cresol p-Cresol p-Methoxyphenol m-Methoxyphenol Xylenol p-Chlorophenol 8 o-Chlorophenol 2,4-dichlorophenol 2-naphthol Hydroquinone Resorcinol The compound of the Formula I may be obtained by stirring the mixture of a compound of the Formula VII with a compound of the Formula VIII at a temperature of 30 to 250 C. and preferably of 50 to C. using an excess amount of the compound of the Formula VH1 as a solvent. It is preferred to add potassium hydroxide or sodium hydroxide as an acid binding agent. If necessary, the reaction may be carried out in the presence of an inert solvent.

(3) PROCESS (3) Examples of a compound of the Formula 1X are as follows:

N-acetylamino-4-hydroxynaphthalimide N- (methylacetylamino -4-hydroxynaphthalimide N- (ethylacetylamino -4-hydroxynaphthalimide N- (butylacetylamino) -4-hydroxynaphthalimide N- 2-methoxyethy1acetylamino) -4-hydroxynaphthalimide N-benzoylamino-4-hydroxynaphthalimide N- (methylb enzoylamino -4-hydroxynaphthalimide N- ethylbenzoylamino -4-hydroxynaphthalimide N- (p-chlorobenzoylamino -4-hydroxynaphthalimide N- (p-toluylamino)-4-hydroxynaphthalimide N- (methyl-p-toluylamino) -4-hydroxynaphthalimide N- (ethyl-p-toluylamino -4-hydroxynaphthalimide N-ureido-4-hydroxynaphthalimide N-( 3 -methylureido -4-hydroxynaphthalimide N- 3-phenylureido -4-hydroxynaphthalimide N- 1,3-dimethy1ureido -4-hydroxynaphthalimide N-ethoxycarbonylamino-4-hydroxynaphthalimide N-phenoxycarbonylamino-4-hydroxynaphthalimide N-tosylamino-4-hydroxynaphthalimide Examples of the alkylating agent include a halogenated alkyl such as methyl chloride methyl bromide methyl iodide ethyl chloride ethyl bromide ethylene dibromide propyl chloride butyl bromide benzyl chloride benzyl bromide ethylene chlorohydrin an ester such as dimethyl sulfate diethyl sulfate dibutyl sulfate methyl p-toluenesulfonate ethyl p-toluenesulfonate butyl p-toluenesnlfonate Z-methoxyethyl p-toluenesulfonate 2-ethoxyethyl p-toluenesulfonate 2-butoxyethyl p-toluenesulfonate an expoxy ring-containing compound such as ethylene oxide propylene oxide, or epichlorohydrin or an active vinyl group-containing compound such as acrylonitrile, or acrylamide A condensation may be accomplished by stirring the mixture of the compound of the Formula IX and the alkylatmg agent in an aqueous solvent at a temperature 9 10 of to 150 C., if necessary, by the addition of sodium NHCOCHiCHBCI hydroxide, potassium hydroxide, sodium carbonate or sodium acetate. 0

(4 PROCESS 4 I" A halogenated compound of the formula X or XI can 5 be produced by the processes (1), (2) or (3) as described above.

Examples of the compound of the Formula X or X] are as follows:

cm 1 11100015201 N o o 1;:110 ocmcrmsr N nnooomol 1|I o o r moocmcnzcl N 0.. To

NHCOCHQCI 1 IIIHCOCHaCHCH Cl o o N NHCOCHaCl NHCOCH=CHC H201 l nooomcl NBC o-Q-cmm z 0 g o I OH NHCOCH 20 As the amine, tertiary, secondary and primary amines and ammonia may be used. Examples of tertiary amines are as follows:

T rimethl amine Triethylamine Diethylmethylamine Diethanolmethylamine Bis (fl-cyanoethyl methylamine Dirnethylcyclohexylamine N-methylyrrolidine N-methylpiperidine N-methylmorpholine Dimethylaniline Pyridine Picoline Quinoline Triethylenediamine Examples of secondary amines are as follows:

Dimethylamine Diethylamine Diethanolamine Pyrrolidine Piperidine Morpholine N-methylaniline Examples of primary amines are al'kylamines such as methylamine ethylamine n-propylamine n-butylarnine, etc. cycloalkylamines such as cyclohexylamine, etc. aralkylamines such as benzylamine, etc. and aromatic amines such as aniline toluidine anisidine naphthylamines, etc. diamines such as ethylenediamine 1,3-propanediamine phenylenediarnine, and 4,4'-diaminodiphenyl ether Examples of hydrazine derivatives are hydrazine, hydrazine hydrate, methylhydrazine, ethylhydrazine, N,N- dimethylhydrazine, N-methyl-N-phenylhydrazine, N-aminopyrrolidine, phenylhydrazine, p-chlorophenylhydrazine and various salts thereof such as hydrochloride, sulfate, etc. thereof.

A reaction of an active halogen atom-containing naphthalimide of the Formula X or XI with an amine may be accomplished at a temperature of 0 to C. in the presence or absence of a solvent. If necessary, the reaction may be carried out at elevated pressures although it is usually carried out at normal pressure. As a solvent, water, alcohols such as methanol, ethanol, etc., ketones such as acetone, methyl isobutyl ketone, etc., ethers such as ethyl ether, dioxane, etc., dimethylformamide or dimethylsulfoxide and aromatic solvents such as benzene, toluene, chlorobenzene, etc. and mixtures thereof may be used.

Thus, naphthalimide compounds of the Formula I are produced by the process (1), (2), (3) or (4), and if necessary, the non-quaternized compounds among them may be successively treated with an alkylating agent or a quaternizing agent to obtain the corresponding quaternized product.

As the alkylating agent or the quaternizing agent, all of known alkylating agents or quaternizing agents may be used. Examples of those agents are as follows:

Esters such as dimethyl sulfate diethyl sulfate methyl p-toluenesulfonate methyl benzenesulfonate, 6W,

Halogenated alkyls such as methyl iodide methyl bromide ethyl bromide, etc.

Acrylic acid derivatives such as acrylonitrile acrylamide methyl acrylate, etc.

The alkylation or quaternization is usually carried out at a temperature of to 200 C. The reaction may be eflected by directly adding an alkylating or a quaternizing agent to the reaction mixture after the previous processes (1) to (4). Alternatively, the compound obtained in the previous processes (1) to (4) may be recovered and then dispersed or dissolved in a fresh solvent to effect the alkylation or quaternization.

The compounds of the Formulas II, VII and IX used in the above-mentioned processes (1) to (4) are all novel compounds which can be easily produced by reacting the corresponding naphthalic anhydride with the corresponding hydrazine compound in the presence or absence of a solvent.

All of the novel naphthalimide derivatives thus obtained according to the present invention may be used as a valuable optical brightening agent. According to the conventional method, the present compound may be fixed onto or dispersed in fibrous materials or resinous materials consisting of polyester, polyacrylonitrile, polyamide, polyether, polyolefin, polyimide, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, acryl, methacryl, epoxy, cellulose ester, cellulose ether, polyvinyl alcohol, polystyrene, polyurethane, polycarbonate, polyacetal, ABS polymer or alkyd, phenol, xylene, urea, melamine, coumarone-indene, silicone or fluorine-containing resin, and the resulting materials show a strong fluorescence of violet to blue under daylight or ultraviolet ray.

A method for optically brightening fibers with the present compounds will be explained below in more detail.

The optical brightening of fibers is advantageously carried out in an aqueous solution or dispersion. For ex ample, fibers are dipped in an aqueous solution or dispersion of the present compounds with heating so that the compounds may be absorbed by the fibers (dip dyeing method). Alternatively, fibers are dipped in an aqueous solution or dispersion of the present compounds till a certain amount of the compounds are exhausted and are then dried and heated to a temperature of 100 C. or higher to be fixed onto the fibers (thermosol method). An appropriate surface active agent, a carrier, other auxiliary agents or additives as well as an oxidizing agent, a bleaching agent, etc. may be added to accomplish the object of the present invention eflfectively. Also, if desired, the optical brightening may be carried out in combination with resin finishing, dyeing, etc.

The present compounds are so stable to heat that they may be applied to so-called dope dyeing method, that is, by adding the presnt compounds to a molten polymeric material before spinning.

The present compounds can be also applied to various plastics other than fibers to produce a remarkable brightening effect. Concretely, the compounds may be applied by known methods such as dry blend method, master powder method, masterbatch method, coating method, etc. Also, optically brightened polymer materials can be produced by adding the present compounds alone or in admixture with various additives to the reaction mixture during the polymerization of a prepolymer or the copolymerization.

As described above, the present compounds are very useful in the optical brightening of organic polymer materials. The optical brightening can be sufnciently accomplished by using a very small amount such as 0.001 to 0.05% of the present compounds based on the material to be brightened. Of course, a further excellent effect can be expected if a larger amount of the present compounds are used.

As is clear from the above description, the optical brightening with the present compounds may be carried out at any stage, that is, before, during or after the forming of organic polymer materials.

The following examples will serve to illustrate the practice of the present invention in more detail but should not be construed to limit the scope of the invention.

In these examples, all parts are expressed by weight unless otherwise indicated.

Example 1 To 1,000 parts by volume of acetic acid, 66.6 parts of N-amino-4-methoxynaphthalimide was added. Further, 66.9 parts of potassium cyanate was added and the mixture was stirred for three hours at room temperature. The separated crystals were recovered by filtration, and washed with a small amount of acetic acid and then with water, and were then dried. Thus, 56.3 parts of N-ureido- 4-methoxynaphthalimide represented by the formula,

NHCONH:

having a melting point of 303 to 305 C. was obtained.

Example 2 N'HC ONHCHs N O- O OCH;

having a melting point of 300 to 301 C. was obtained.

The following compounds were produced by reacting the compounds of the Formula II with isocyanic acid derivatives as indicated below in the same manner as in Example 2.

Formula II Example No.

Meltin R R Isoeyauic acid derivative Product point C.

3 CH3 H Pheuyl isocyanate 310312 IIIHC ONH- N O=( ]:o

4..:::: CzHn CH3 Methyl isocyanate.

5. CH H Xylyleue diisocyanate- ;'.T.- 260-251 NH O O NHCH l; CHaNHO 01 n: O O N 6. CH H Hexamethylene diisoeyanate IIIHC ONHCH;(CH2)4CH;NHC OIIIH 231-235 N N f O CH 0 CH CH3 CH3 6O i N of o Example 8 65 Into a suspension of 2.0 parts of N-methylamino-4- methoxynaphthalimide in 20 parts of acetone, 1.8 parts of o-toluyl chloride was added. The mixture was stirred for 20 hours at room temperature and was then concen- 7 trated under reduced pressure. The residue was recrystalo o lized from ethanol. Thus, 2.2 parts of N-(methyl-o- 'i g a melt-mg palm of 179 to 180 was obtamfad' e following compounds were produced by reacting toluylamino)-4-meth0XYnaPhtha1imide represented y the the compounds of the Formula II with acid halides as formula, 75 indicated below in the same mauner'as in Example 8.

3 2 mo m o aofio dgs 58 m o mofio mm 27%: USMC 00 N t $228 EQ EO m c 7 Na EN SN 00 m 2 3 m 3.22% Efifim m 1260. ms 06mm 4w 6 2.22 mo 00 m O QE QS E84 m 8 2 8 O co M ED SVE 335m m 56 2 mNL-mm mo 00 m m o @FECE; T3004 m ammo wn mm w 550 00 E E0 Q2850 338850 m O U/ 0 8X 0 o co m mo QESEQ 28 Bianca N "we 8 3? 00 m in -6362 EQEESOEQQ m E0 2 NE SN 5 00 M NO 02.650 30238030 m 50 omalmmm 00 m "m6 In 52.830 320 b M ED 5 aomA 00 m "NO 03850 E QEQ M 2 53% co m mo 3250 55am m m5 u u "mo 00 m 50 2825 584 M mo 1.... mnwlhmw 00 HH HMO arr-C T3004 m "m a av QM 8 SH M 5m M a 3 4 E M 2 E H 2: 525

H 2 M G nnno 02 mo 00 MENU QHHOONHHONEU k if E... "mo mmO G Nm w uwn u w mm c3153 3WD 00 m0 Q @535; T334 HF QTEH 00 E6 E0 Q23 0 E an 5 E5 3723 "MO 00 m6 SW5 IlaI-iu {1-1. Q S Q 384 m $72: Q 00 mmO MO 62.650 3325 N 00.7mm mo 00 W O WHO cc c H534 mmmo "m mfilmfi "NO 00 "MO .mH O 63.850 $309 8 0 37E; "MO 00 50 m5 iv. dwto Q 332: E0 @818 6 00 E0 E5 -dug o EOE EQ d STQQH 00 E0 M5 I. dES O hosmmpfio o E0 E5 bwfilmfi Q 00 "m0 mmo 7 cc m0 N @263 O0 MOEOEO QMO 2. .J 02.830 $85 MOEOSMO ca m: -OHU 00 $10 QHHNO w mmo m O 3 Q0 0v Q5 s mm W mu mn mi s 204 M m z gamma mm 3 5222 5 2259 G 225cm 31 Example 54 To 300 parts by volume of toluene, 20 parts of N-amino- 4-ethoxynaphtha1imide was added. Further, 24 parts of acetic anhydride was added, and the mixture was stirred 32 Example 64 500 parts of phthalic anhydride was molten at 140 C.,

to which 78.7 parts of N-amino-4-methoxynaphthalimide was added. The mixture was heated to 190 C. in 1'0 for 5 hours at room temperature. The separated crystals 5 minutes and kept at to 195 for one hour- The were recovered by filtration, washed with 300 parts by mixture was allowed to cool to room mp volume of toluene and dried. Thus, 22.6 parts of a com- 10,000 Parts of water added and the mlxture was pound represented by the fo l heated and then filtered while hot. The cake was washed with hot water and dried. The product was then recrystallized from acetic acid. Thus, 81.5 parts of a compound re r ent d b the for 111 NHCOOH: P as e y m N o: o I 00/ N O O fizHs was obtained. The product showed a melting point of 248 m to 249 C. and the wave length of maximum ultraviolet absorption in 3eganol solution thereof showlng blue fluowas obtained The Product had a melting point of ,23 H d f h l f 1 to 312 C. and showed blue fluorescence. The wavelength e 0 owmg compoun s o t e genera ormu of maximum ultraviolet absorption in ethanol solution thereof was 366 my.

The following compounds of the general formula,

I N Y z of To Ow where obtained by reacting the compounds of the Formula were produced by reacting the compounds of the Formula II with acid anhydrides as indicated below in the same II wherein R is hydrogen with acid auhydrides as indimanner as in Example 54. cated below in the same manner as in Example 64.

Formula II Above formula Melting R R1 Acid anhydride R R1 Y R; 5

Example number:

CH: Acetic anhydride OH; H CO CH; 257-259 56 OH; H Benzolc anhydride CH1 00 Q 226-227 57 Q E Acetic anhydride Q H CO CH3 137-140 58 CHzCHzOCqHn H d0 CHzCHgOQgHo H CO CH: 138140 CH3 0113 ...do CH CH CO CH; 245-246 CH3 do 01H CH3 CO CH; 171-172 01H; do. CH3 02H; 00 CH; 158-160 0211 do. 02H; 01H. 00 CH; 137-139 CH do CHzCHzOCHa 0H, 00 CH 0 Above formula Melting R in Formula II Acid anhydrlde R A Example number:

65 CH; Dichlorophthallc auhydrlde CH Cl 300 66 CH Tetreohlorophthallo auhydrlde.. OH; (ill 300 67 CH Tetrabromophthallc anhydrlde- CH; Br 300 68 OH; Napthalle anhydrlde..- Q 300 Maleie anhydrlde. CH CH=CH Suecinic anhydrlde- CH -CH3CHrl 71 CHzCHzOCaHa Phthallc anhydrlde 011 011 00 11. Q 201.203

Iii-CO N O 0 Example 72 A mixture of 3.7 parts of N (methylbenzoylanfino) 4 chloronaphthalimide, 20 parts of ethanol and 0.6 part of potassium hydroxide was heated for 10 hours under reflux. The mixture was then allowed to cool to room tem- 0,11 perature and a small amount of water was added thereto. The separated crystals were recovered by filtration, having a melting pomt 145 to 147 C. was obtained.

washed with water and dried. Thus, N-(methylbenzoyl- The following compounds were produced by reacting amino) 4 ethoxynaphthalimide represented by the the compounds of the Formula VII with the compounds formula, of the Formula VIII in the same manner as in Example 72.

F ul VII El N(per out) R; R; X FormulaVIII Product Found Calcd.

Example number:

73 CH; CH: Cl CHaOH H| 9.39 9.26

TABLE-Continued Formula VII Formula VIII Elementary analysis N(pereent) Product Found Caled;

Example number:

CH; Cl

( z u) zN-CHzCHgOH Example 80 2.5 parts of N-acetylamino-thydroxynaphthalimide (M.P. 306 to 307 C.) was dissolved in an aqueous solution of 3.0 parts of sodium hydroxide in 20 parts of water and parts by volume of methanol was added thereto. The mixture was cooled to C. 3.7 parts of dimethyl sulfate was gradually dropped into the mixture in 5 hours. After the completion of dropping, the mixture was stirred for 5 hours at room temperature and was then acidified strongly with hydrochloric acid. The separated crystals were recovered by filtration and were then recrystallized from glacial acetic acid. Thus, N-acetylamino 4 methoxynaphthalimide represented by the formula,

NHCOCH:

Alkylati z 1 agent, Product 81 /C;H (0 1103304 /CIHI \C O CH; N CO CH.

CHI Q-cmcx N\ \C 0 CH: 11 CO CH;

Q 83-..:-.-- cm CHr-CH: on,

"CO@ N CHICHQOH TABLE-Continued Ex. X in formula Alkylatlng No. IX agent Product 84"... CH; CH;

CH s Or-O-CHzCHg ()CH N o o CHaCHzO CH;

85..... CHaBr -NHCO 11130 0- N 0 To EXAMPLE 86 ray. Also, when polyacrylonitrile fibers were dyed with OT 0 Q was obtained in a quantitative yield.

The Wave length of maximum absorption in aqueous solution thereof was 376 my. and the solution showed strong blue fluorescence under daylight and ultraviolet the product according to a usual method, remarkably brilliant white dyeings were obtained.

The wave length of maximum ultraviolet absorption (A of the compounds which were produced by reacting the compounds of the Formula X with tertiary nitrogen atom-containing amines or hydrazines in the same manner as in Example 86 and the color of fluorescence on polyacrylonitrile fibers obtained by dyeing the fibers with the respective compound according to a usual method are shown in the following table.

In Formula X n=1, Y= 00 Color 0! fluorescence Ex. km on pqlyacry- No. R R1 R; Z Amine or hydrazine (m lonitnle fibers 87 --:CH| H CH: C1 Pyridine 378 Blue.

88.... CH; H CH: 01 Dimethylhydrazine 378 D0. 89...- OH: H CH; 01 Triethylenediamine 377 Do. 90.--- CH: CH1 CH: 01 379 Do.

91.. CH: CH: CH2 Cl 378 Do.

92-. CH1 CH1 CH Cl 379 Do.

93-. 02H; H CH: Cl 379 Do.

94-. CaH5 CH: CH: Cl 379 D0.

95.. C2H5 02H; CH2 Cl 375 13 0. 96---....- CsHt H CH: 01 370 Reddlsh blue. 

